TWI513723B - Process for continuous preparation of a prepolymer based on phenolic resins, oxazolines and epoxides - Google Patents

Description

Method for continuously preparing prepolymer based on phenolic resin, oxazoline and epoxide

The present invention describes a continuous preparation based on the use of a catalyst A method of prepolymerizing oxazolines, epoxides and phenolic resins, and uses thereof.

EA Boulter et al., Electrical Insulation Conference, 1997, and Electrical Manufacturing & Coil Winding Conference Proceedings, Vol. 22-25 (September 1997), pages 249-253, describe The properties of azoline-modified phenolic resins, such as, for example, adhesion to carbon fibers, glass fibers and metals, resistance to thermal oxidative degradation, small amounts of fumes, low flammability and high impact strength during fire events . Due to this low flammability, these polymers are particularly suitable for the manufacture of components in the aerospace industry. Other applications are in the field of electrical insulation and electronic instrumentation. According to EA Boulter, these precursors and prepolymers are also suitable for applications including injection molding, resin transfer molding (RTM) and prepregs.

Bifunctional groups are described in the literature. The reaction of oxazolines with phenolic resins. For example, the patent specification US 4,699,970 describes phenolic resins with 1,3-phenylene double The reaction of oxazoline in the presence of a catalytic amount of triphenyl phosphite. According to the examples, curing was carried out at a temperature of 225 °C. The polymer obtained had a glass transition temperature of 138 to 184 °C.

US 5,302,687 also describes 1,3-phenylene double The reaction of an oxazoline with a phenolic resin in the presence of a phosphonium salt and/or an ammonium salt. The curing was also carried out here at 225 ° C according to the examples, and the polymer likewise had a glass transition temperature of 150 to 157 °C.

WO 2009/132924 describes a polymer composition containing a phenolic resin, the polymer composition comprising Oxazolines and stabilizers. The catalyst used is a trialkyl phosphite or a triaryl phosphite. The polymer composition is preferably prepared by an extruder.

WO 2009/053581 describes a resin composition composed of an epoxy resin and a plasticizer, which has a function of dissolving the epoxy resin and affects the viscosity.

The resin composition may, for example, additionally be combined with a crosslinking agent such as 1,3-phenylene The oxazoline is blended. The catalyst used includes, for example, Lewis bases and Lewis acids such as boron trifluoride-monoethylamine. The composition can be prepared by simple mixing. The curing temperature is not higher than 195 °C.

Hajime Kimura et al. in Journal of Applied Polymer Science, Vol. 107, pp. 710-718 (2008) described by Double Oxazolines and benzo A method of preparing a resin composition of the like, which uses a mixture of a sulfonic acid and an amino alcohol or an alkylamine as a catalyst (potential sulfonic acid). The resin was prepared by a batch process. The polymer obtained had a glass transition temperature between 149 and 186 °C.

It is an object of the present invention to provide a phenolic resin-based prepolymer characterized by high solubility in ketones and melting point below 100 °C. The prepolymer should be more particularly suitable for the manufacture of materials having a glass transition temperature ( _Tg ) in the range of from 140 to 200 °C.

Surprisingly, it has been discovered by A continuous process for the preparation of prepolymers from oxazoline components, phenolic resins, epoxides and catalysts. Due to the use of a catalyst, the prepolymer can be prepared at lower curing temperatures and/or can reduce cure time compared to prior art methods. The resulting polymer is characterized by a glass transition temperature T _{g of} from 140 to 200 °C.

It has furthermore been shown that the prepolymers of the invention can be prepared continuously by extrusion. Extrusion surprisingly brings the possibility of a prepolymer that is substantially free of pre-crosslinking, relative to the batch process set forth in the prior art. The application of an extruder that separately measures the starting material from the point of view of time and position from the point of view of the time and position can almost completely avoid any unwanted premature reaction. The prepolymer which is rapidly cooled by the freezing belt after being discharged from the mold terminates the reaction. Thus, a prepolymer having a very low degree of crosslinking and its homogeneity is obtained, and thus the prepolymer is very soluble in standard commercial solvents such as, for example, ketones. The process of the invention also allows the prepolymer of the invention to have consistent product properties.

Regarding the use of prepolymers in resin transfer molding (RTM) systems, such as for solution processing, for glass fiber coating, or for the manufacture of prepregs, it is necessary to obtain a gel-free material. Materials previously prepared in batches are insoluble in standard commercial solvents and have no melting point. Conversely, the prepolymers of the present invention are soluble in standard commercial solvents without substantial residue and can therefore be readily processed further. Furthermore, the prepolymer of the present invention can be applied to the manufacture of structural components including the electrical laminate, transportation, and aerospace industries.

Therefore, the present invention provides a continuous preparation of a phenolic resin based on the presence of a catalyst. a method of pre-polymerizing an oxazoline component and an epoxide, the method characterized by the phenolic resin in stream A and The oxazoline component is supplied to the extruder; and the Lewis B adduct of boron trifluoride or aluminum trichloride as a catalyst, or the arylsulfonic acid or alkanesulfonic acid, or a latent aromatic sulfonic acid Or a potential alkane sulfonic acid is supplied to the extruder; and the epoxide is supplied to the extruder in stream C, the lateral feed of the stream A being attached to the stream C when viewed in the direction of extrusion Prior to the transverse feed, the reactants are mixed at a reaction temperature of 120 to 200 ° C and a residence time of 3 seconds to 15 minutes in the extruder; and then the extruder is placed within 30 to 60 seconds. The effluent product was cooled to a temperature below 45 °C.

The invention further provides a prepolymer prepared by the process of the invention and the use of the prepolymer of the invention.

For the purposes of the present invention, a prepolymer is understood to be an oligomeric compound which is predominantly also a small proportion of polymeric compound. The prepolymer is also soluble and malleable relative to the polymer and is fundamentally convertible to the target polymer by a thermal initiation reaction. The term "potential arylsulfonic acid" or "potential alkane sulfonic acid" is understood to mean a mixture of sulfonic acid and an amino alcohol or an alkylamine.

The method of the present invention is preferably used in accordance with the following structure (1) Oxazoline Oxazoline component

Wherein R ¹ =C _1-2 alkyl or phenyl, R ² , R ³ and R ⁿ = hydrogen, C _1-2 alkyl, g=0, 1, 2, 3, and/or according to structure (2) Double Oxazoline

Wherein A = methylene or phenyl, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ^m , R ^o = hydrogen, C _1-2 alkyl, h, i = 0, 1, 2, 3, The substituents of the R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁿ , R ^m and R ^o type may be the same or different and substituted or unsubstituted, and the structural moiety A may be Substituted or unsubstituted, and m and o may be the same or different.

The structural fragment A may have a methyl group and/or an ethyl group as a substituent. The substituents of the R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁿ , R ^m and R ^o type are preferably unsubstituted.

The method of the present invention preferably uses a substituent having R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁿ , R ^m and R ^o type and an unsubstituted structural moiety A. A compound according to structure (1) and/or (2). It is preferred to use a compound according to the structures (1) and/or (2) and g, h, i = 0 or 1.

A preferred embodiment of the method of the present invention uses a double according to the structure (2) Oxazolines, wherein m and o are preferably 0 or 1. More particularly, the use of structural segment A has a structure based on the structure of the phenyl group (2) Oxazoline, such as 1,3-phenylene Oxazoline or 1,4-phenylene double Oxazoline. In order to customize the properties of the prepolymer, it can also be used Oxazoline and double a mixture of oxazolines Oxazoline component.

In the method of the present invention, it is preferred to use 10% by weight to 90% by weight, preferably 30% by weight to 60% by weight and more preferably 40% by weight to 55% by weight based on the composition of the starting material. Oxazoline component.

In the method of the present invention, a phenol resin obtained by condensing a phenol with an aldehyde, more specifically formaldehyde, is preferably used. Therefore, a phenol resin selected from the group consisting of a novolac resin type and/or a resol type resin can be used in this method. It is particularly preferable to use a novolak resin as the phenol resin (B). In the method of the present invention, it is preferred to use 10% by weight to 90% by weight, preferably 30% by weight to 60% by weight and more preferably 40% by weight to 50% by weight, based on the composition of the starting material, of the phenolic resin. .

With regard to the epoxide, a monoepoxide according to structure (3) can be used in the process of the invention.

Wherein R ⁸ = hydrogen, C _1-3 alkyl, the diepoxide of structure (4)

Wherein R ⁹ and R ¹⁰ = hydrogen and C _1-3 alkyl, R ⁹ and R ¹⁰ may be the same or different, or a polyfunctional epoxide according to structure (5) and/or structure (6)

Wherein R ¹¹ = hydrogen, C _1-3 alkyl or

Wherein R ¹² = hydrogen or C _1-3 alkyl.

It is preferred in the process of the invention to use a mixture of monoepoxides, diepoxides and/or polyepoxides as the epoxide. The structures (3) and (6) preferably have a linear alkyl group.

Preferably, in the process of the present invention, from 1% by weight to 10% by weight, preferably from 3% by weight to 8% by weight and more preferably from 4% by weight to 6% by weight, based on the composition of the starting material, of the epoxide .

The benzoic acid of structure (7) may also be additionally supplied in a specific embodiment of the method of the invention. class

Where A=(CR ¹³ R ¹⁴ ), S

R ¹³ , R ¹⁴ =H, C _1-4 alkyl

To the extruder. In the region of 180 to 190 ° C, these compounds are rearranged to provide an OH group of other phenols for reaction.

Preferably, the process of the invention is based on the composition of the starting materials, from 0% to 10% by weight, preferably from 2% to 9% by weight and more preferably from 4% to 8% by weight. Oxazolines. No benzoic acid is used in a particular embodiment of the method of the invention .

With respect to the catalyst in the process of the present invention, it is preferred to use a Lewis Additive of boron trichloride or a latent arylsulfonic acid, more particularly a boron trifluoride-ethylamine adduct, trifluoroethylene. Boron-methanol adduct, boron trifluoride-phosphoric acid, p-toluenesulfonic acid/diethanolamine or p-toluenesulfonic acid/1-amino-2-propanol. The Lewis autoclave of boron trifluoride emits BF ₃ at elevated temperatures. The direct use of BF ₃ in the process of the invention is not appropriate due to the gaseous state and its toxicity. AlCl ₃ adducts can also be used with regard to alternatives. For the purposes of the present invention, potential aryl sulfonic acids are adducts of sulfonic acids and donor compounds. More particularly, the donor compound is an amine alcohol or an alkylamine having from 1 to 4 carbon atoms. The latent aryl sulfonic acid is particularly preferably an equimolar mixture of a sulfonic acid and an amino alcohol or an alkylamine, preferably an amine alcohol. Without being bound by theory, it is assumed that the case of potential aryl sulfonic acids will release catalytically active sulfonic acids at elevated temperatures.

The catalyst in the process of the present invention is preferably used in an amount of from 0.2% by weight to 5% by weight, preferably from 0.4% by weight to 4% by weight and more preferably from 0.5% by weight to 3% by weight, based on the composition of the starting materials.

It is beneficial to supply the Lewis Lewis adduct catalyst in solution to the extruder. In the process of the present invention, the catalyst is preferably an alcohol solution, more preferably an ethanol solution. The amount of the catalyst in the alcohol is preferably from 30% by weight to 50% by weight. When arylsulfonic acids or alkanesulfonic acids are used as the catalyst, either alone or in the presence of a latent aryl sulfonic acid, it is beneficial to meter it into the extruder as a melt.

In the process of the invention, the catalyst is also the same, and an antioxidant may also be added, preferably in accordance with the lateral feed of the starting material into the extruder. As the antioxidant, it is preferred to use a so-called sterically hindered phenol, which is preferably a compound according to the structure (8).

Wherein R _a , R _b , R _c = hydrogen, alkyl, alkaryl or cycloalkyl, the substituents of the R _a , R _b , R _c type may be the same or different and substituted or unsubstituted, as , for example, a reaction product of 4-methylphenol with dicyclopentadiene and isobutylene according to structure (9),

Where p = 1 to 5.

The antioxidant is preferably used in the process of the invention in an amount of from 0.1% by weight to 2% by weight, preferably from 0.2% by weight to 1.5% by weight and more preferably from 0.2% by weight to 1.2% by weight, based on the composition of the starting materials. An example of an antioxidant that can be used is LC or LC.

In the method of the present invention, a stabilizer may also be additionally used, preferably a so-called HALS compound (hindered amine light stabilizer)-2,2,6,6-tetramethylhexahydropyridin-4-one derivative is used. . Mixtures of different HALS compounds can also be added. The addition of a stabilizer can improve the long-term stability of the resulting polymer.

Preferably, the stabilizer according to structure (10) is used in the method of the present invention.

Wherein R ^' = alkoxy, , and R ^” = oxygen radical (-O‧), hydrogen, alkyl or alkoxy,

Wherein R''' and R ^IV = alkyl, R ^V = heterocyclic ring and A'=alkylene group, and wherein the alkyl group, alkoxy group and alkylene group and heterocyclic ring are substituted or unsubstituted.

It is particularly preferred in the process of the invention to use stabilizers according to the following structures (11) to (13):

Wherein R ^VII = hydrogen, alkyl or alkoxy,

Where R ^VI = q=2 to 10, or

Wherein R ^VIII = hydrogen or alkyl.

Another embodiment of the method of the invention uses a so-called polymer-bound HALS compound, such as, for example, a compound according to structure (14)

Wherein R ^IX = hydrogen or alkyl and r, s 10.

These polymer-bonded HALS compounds are 2,2,6,6-tetramethylhexahydropyridin-4-one derivatives bonded to or in the polymer chain.

In particular, the stabilizer is used in the process of the invention on the basis of the composition of the starting materials, using from 0.1% by weight to 2% by weight, preferably from 0.2% by weight to 1.5% by weight and more preferably from 0.3% by weight to 1.2% by weight. the amount.

In the process of the present invention, it is preferred to incorporate not only the sterically hindered phenols but also the HALS compound into the starting materials.

In another embodiment of the method of the present invention, the stabilizer and/or antioxidant can be subsequently blended into the prepolymer in a downstream assembly.

It is advantageous in the process of the invention to add an additive such as, for example, a devolatilizer, a defoaming agent or a so-called flow control additive to the starting material. About the additive can be used by, for example, BYK under the trade name -A 506, -A 525, -A 530, BYK-054, -R 605, -R 606 or -A 535 sold, such as eucalyptus or fluorenone modified polyglycols and polyethers, defoaming polyoxyalkylenes or polymers, polyether modified polymethylalkyl oxime Alkanes. The addition of these additives has the advantage of significantly reducing the formation of bubbles in the prepolymer and subsequent materials. The additive or a mixture of two or more of these additives is preferably based on the composition of the starting material, from 0.1% by weight to 1% by weight, preferably from 0.2% by weight to 0.8% by weight, and preferably from 0.3% by weight to 0.7% by weight. The amount of % is added.

Further, a halogenated and non-halogenated flame retardant may be added to the prepolymer, and in the method of the present invention, it is preferred to use 1% by weight to 10% by weight of the flame retardant based on the composition of the starting material. .

When using the prepolymer solution of the present invention, it is recommended to add a flow control agent, a wetting agent, a devolatilizer, other solvents, and inorganic additives, such as precipitated cerium oxide, to improve the discrimination criteria, including surface adhesion. , leveling and fire resistance. Therefore, in the method of the present invention, it is preferred to use 0.5% by weight to 5% by weight, more preferably 2% by weight to 4% by weight, based on the composition of the starting material, of precipitated cerium oxide, which is , for example, by product name 50 types of sale.

Other additives come from the field of impact modifiers; therefore, in the process of the invention, the composition of the starting materials can be used as a basis, for example, from 1% by weight to 15% by weight of the impact modifier.

Furthermore, it is beneficial to use at least one release agent in the process of the invention. This allows an improvement in the management of the polymer composition in the forming process. In the method of the present invention, it is preferred to use a release agent selected from the group consisting of

- polyoxane, in the form of, for example, oil, oil emulsion in water, fat and resin,

- waxes, examples of natural and synthetic alkanes with and without functional groups,

- metal soaps or metal salts of fatty acids such as calcium stearate, lead, magnesium, aluminum and/or zinc,

- grease,

- Polymers, examples being polyvinyl alcohols, polyesters and polyolefins,

- Phosphate monoesters,

- Fluorinated hydrocarbons and / or

- Inorganic release agents such as graphite powder, talc and mica powder.

The prepolymer prepared by the process of the present invention preferably comprises an internal release agent system which is added to the starting material of the process of the invention and which is mainly accumulated in the molding during the forming operation. The surface may or may cause a faster cure of the surface to prevent any bond between the mold wall and the molded article. More particularly in the process of the invention is the use of a release agent from Acmos Chemie KG, which is sold under the trade name 82-837, 82-847, 82-860, 82-866, 82-9018 and 82-853 is for sale. In the process of the invention, the release agent is more preferably used in an amount of from 0.1% by weight to 2% by weight, very preferably from 0.2% by weight to 1.5% by weight, based on the composition of the starting material.

Further, a wetting agent, preferably a surfactant, more preferably an ethoxylated group, based on the composition of the starting material, preferably in an amount of from 0.1% by weight to 2% by weight, may be used in the process. Fatty alcohols or sodium lauryl sulfate.

The intensive mixing of the starting materials in the process of the invention is accomplished by heating in an extruder. The intensive mixing and transient reaction with the heating means that the residence time of the starting material in the extruder is usually from 3 seconds to 15 minutes, preferably from 3 seconds to 5 minutes, more preferably from 5 to 180 seconds, and very good. It is 30 to 90 seconds. During this period the starting material cooperates with heat for a brief but intense mixing and may partially cause a reaction. These retention time and temperature patterns may vary depending on the nature of the starting materials and the final product.

Since the object of the process of the invention is to prepare a prepolymer, it is preferred to use the selected temperature, residence time and supply of the stream to achieve The oxazoline is based on a conversion of no more than 5%. In a particularly preferred embodiment of one of the methods of the invention, there is no conversion.

Equipment such as single or multi-screw extruders, more particularly twin-screw extruders, planetary roller extruders or ring-shaped extruders, are particularly suitable for use in the extruder of the process of the invention and are preferred By. A multi-axis extruder, such as a ring extruder, can be used in a particular embodiment of the process of the invention. It is particularly preferred to use a multi-screw extruder, more particularly a twin-screw extruder, and a multi-axis extruder, more particularly a ring extruder. Especially preferred is a twin screw extruder.

Preferably, the starting material is metered into the extruder in a separate stream to prevent premature curing of the prepolymer. Therefore, it is preferred to use a multi-cylinder extruder. A multi-cylinder extruder for the purpose of the present invention means that the sleeve surrounding the screw is divided into different zones which can be separately heated or cooled. In these different zones, referred to as cartridges, the streams may also be supplied separately from the other. In this way, the streams can be explicitly supplied to different locations of the extruder, and the composition of the individual streams can vary.

Figure 1 schematically depicts an exemplary construction of this multi-cylinder extruder;

(a) Measurement supply of logistics A

(b) Measurement supply of logistics B

(c) Product discharge position (measurement position of outlet temperature)

(d) Cooling belt

(e) Granulator

(f) Fine particles

(g) a sleeve divided into 8 different zones (known as cartridges)

(h) Screw drive

(i) the head of the extruder (measurement position of the head temperature)

(k) Measurement supply of logistics C

The different barrels of the extruder of the process of the invention preferably have different temperatures. The cylinder just adjacent to the screw drive preferably has a temperature lower than the reaction temperature (temperature zone TZ1), more preferably 30 to 100 °C. The cylinder at the discharge position of the product has a temperature lower than the reaction temperature (temperature zone TZ3), more preferably 100 to 160 °C. The cartridge disposed in the center of the extruder has a desired reaction temperature (temperature zone TZ2) which is 160 to 200 ° C, preferably 170 to 190 ° C and more preferably 175 to 185 ° C in the case of the method of the present invention. .

In the context of the present invention, the term "reaction temperature" means a difference from a reaction characterized by a significant conversion; rather, in the process of the invention, the target is a maximum conversion of 5%, but preferably no conversion.

In the process of the present invention, it is preferred to supply the phenolic resin in a stream A and The oxazoline component is fed to the extruder, preferably in the extruder barrel with temperature zone TZ1 and more preferably in the first cylinder just adjacent to the screw drive.

It is highly advantageous to supply the epoxide and catalyst to the extruder in separate streams B or C, which are preferably fed to the central zone of the temperature zone TZ2 or to the temperature zone. The product of the TZ3 is discharged from the barrel before the position. The feed preferably occurs in the barrel of the temperature zone TZ2 closest to the product discharge location. Preferably, the two streams B and C are supplied separately to the extruder, which is especially beneficial when the catalyst is supplied to the extruder in solution.

In a particular embodiment of the process of the invention, stream B, with the proviso that the catalyst is in a solid state rather than a solution, can be supplied to stream A in front of the extruder, so streams A and B are supplied together to The extruder. The two metered A and B co-metered feeds preferably occur in the temperature zone TZ1, and particularly preferably the co-metered feed occurs in the first cylinder adjacent the screw drive.

A viable additive such as a defoaming agent, a devolatilizer, a stabilizer or an antioxidant, for example, supplied to the extruder is preferably stream A. However, it is also possible to supply the additive to one of the extruders at a supply port other than the two streams A and B.

Subsequent cooling is preferably carried out quickly and can be incorporated into the extruder. In addition, however, tube bundles, coils, chill rolls, air conveyors, and metal conveyor belts can be used downstream of the extruder.

The conversion is initially further cooled to the appropriate temperature by the corresponding apparatus described above, depending on the viscosity of the prepolymer leaving the extruder. Then, it is granulated or pulverized to a desired particle diameter by a crusher, a pin mill, a hammer mill or a tablet rolling mill.

The prepolymer obtained by the process of the invention is characterized by being soluble in ketones, more preferably in 2-butanone, forming a clear solution, with the proviso that no solids are used, such as in the process of the invention The additive precipitates cerium oxide. Further, the prepolymer of the present invention preferably has a melting range of 60 to 120 ° C, preferably 77 to 116 ° C.

These properties of the prepolymer of the present invention distinguish it from the prior art prepolymer which is insoluble in 2-butanone. Furthermore, the products of the prior art cannot measure the melting point because it generally decomposes in advance.

The nature of the prepolymer of the present invention also points to a much lower degree of crosslinking than the products of prior art methods. The prepolymer of the present invention can thus be applied to a support material such as glass fiber or carbon fiber in the form of a solution in a ketone (e.g., such as 2-butanone). The prepolymer is also feasible by powder technology because the prepolymer of the present invention has a melting point and thus can be melted without decomposition.

Further provided by the invention is the use of the prepolymer of the invention for the manufacture of materials, more particularly composite materials, more preferably fiber composite materials. In addition to its use for the manufacture of composite materials, the prepolymers of the invention can also be used to make plastics. These manufactured plastics preferably have a glass transition temperature of 140 to 200 ° C and more preferably 175 to 190 ° C, T _g , and these materials are preferably free of formaldehyde.

Depending on the type of use, the prepolymer of the present invention may be first dissolved in a standard commercial solvent, more particularly a ketone, preferably 2-butanone.

Inorganic reinforcing fibers (for example, glass fibers), organic reinforcing fibers (for example, guanamine fibers), or carbon fibers, metal reinforcing fibers or natural fibers can be used in the inventive use of the above prepolymer. The reinforcing fibers in these cases can be used in the form of woven fabrics, weftless scrims, multiaxial scrims, non-fibrous fabrics, knitted fabrics, webbing or mats.

The prepolymer of the present invention is preferably first dissolved in a ketone, more preferably in 2-butanone, and then impregnated with a solution of the prepolymer of the present invention, preferably a glass fiber or carbon fiber, and finally cured. .

In the context of this invention, the above prepolymer is used as a matrix. Thus the prepolymer can be used, for example, to make prepreg intermediates such as sheet forming materials (SMC) or bulk forming materials (BMC). Preforming can also be used to make intermediates in this inventive use.

The processing of the prepolymer with the reinforcing material to form the composite can be accomplished by a variety of methods/techniques in accordance with prior art techniques. More particularly, the composite is manufactured by one of the techniques listed below:

- cascading, including manual cascading,

- pre-impregnation technology,

- Resin transfer forming (RTM),

- Infusion methods such as resin infusion forming (RIM) or Seeman composite resin infusion (SCRIMP),

- Winding method,

- Pultrusion or

- fibre laying processes.

In this inventive use the prepolymer can be cured by means of a temperature, for example in an oven, in a pressure cooker or in a press, or using microwaves.

Composite materials made by this inventive use are useful in the fields of, inter alia, aerial tourism, transportation (such as the automotive industry) and the electrical industry. These composite materials are used in wind power plants, ducts or in the form of tanks or pressure tanks.

The prepolymers can also be used in the manufacture of lightweight constructions, especially in combination with multilayer constructions such as honeycombs or foams based on phenolic resins, polyimine, glass, polyurethane, polyamide or polyvinyl chloride.

The material for the prepolymer caused particularly having high heat distortion resistance, high glass transition _temperature, T _g component. The high toughness and restoring power of this prepolymer is also beneficial for resulting in improved impact resistance.

Other fields of application of the prepolymer or materials derived from the prepolymer are, for example, abrasives, refractory products, foundry industry, battery separators, compression and injection molding, mineral wool (especially from glass, rock or basalt) (formaldehyde-free) component, paper impregnated, glass or paper-based laminate for electrical insulation, foam or glass or metal coating (for example as cable protection), rubber mixture Used as a substitute for novolacs, as a separate phase and as a co-reactant with other thermosets such as bismaleimide.

The prepolymer of the present invention is preferably useful for making prepregs. For the purpose of the present invention, the prepreg (abbreviated form of prepreg) represents an intermediate product composed of continuous fibers and an uncured matrix composed of the prepolymer of the present invention. Continuous fibers useful in this product include glass fibers, carbon fibers, and guanamine fibers. The prepolymer of the present invention is preferably used in the manufacture of these prepregs in powder form.

The following examples are intended to explain the method of the invention in more detail, and are not intended to limit the invention to this particular embodiment.

Example Comparative Examples 1 to 3:

Mix 14.30g of 1,3-phenylene double in a Brabender W 30 kneading chamber at 160 ° C and 50 rpm Oxazoline, 13.91 g of phenolic resin (from Sumitomo-Bakelite 33100), 1.50 g of epoxide (from Aldrich 506 epoxy resin) and 0.30 g of catalyst. In order to prevent the product from being squeezed out of the barrel, the ram of the kneading apparatus was weighed by a lever to a weight of 1 kg. After just a few minutes, the mixture is no longer kneaded and the mixing operation is stopped. The catalysts and results used are summarized in Table 1.

Conventionally, the mixed components in the kneading chamber cause the melting point or decomposition temperature of the cured product to be higher than 300 ° C and thus it is considered to be incompatible with the prepolymer.

Comparative Examples 4 to 5:

Making 14.30g of 1,3-phenylene double Oxazoline and 13.90 g of phenolic resin (from Sumitomo-Bakelite 33100) Melt in a glass beaker at a bath temperature of 160 ° C for about 30 minutes; then, with stirring, add 1.50 g of epoxide (from Aldrich) 506 epoxy resin) and 0.30 g of catalyst. A few minutes after the addition of the catalyst, the mixture was no longer stirred. The catalysts and results used are summarized in Table 2.

Even if the epoxide and catalyst are later added to the mixture, the melting point or decomposition temperature of the cured product is higher than 300 ° C and thus it is considered to be incompatible with the prepolymer.

Comparative Example 6:

Making 14.30g of 1,3-phenylene double Oxazoline and 13.90 g of phenolic resin (from Sumitomo-Bakelite 33100) Melt in a glass beaker at a bath temperature of 160 ° C for about 30 minutes; then, with stirring, add 1.50 g of epoxide (from Aldrich) 506 epoxy resin) and 0.30 g of triphenyl phosphite as a catalyst. The starting material was stirred for a further 5 minutes and then the melt was allowed to cool to room temperature. The prepolymer had a melting range of 85.5 to 101 ° C and a glass transition temperature T _g of 137 ° C, and the curing was carried out at a temperature of 180 ° C for 6 hours.

A prepolymer obtained using triphenyl phosphite as a catalyst can give a material having a glass transition temperature T _{g of} only 137 °C.

Inventive Examples 7 to 10:

Examples 7 to 10 were carried out in a DSE 25 twin-screw extruder from Brabender consisting of 8 separate heated and cooled cylinders (see Figure 1).

The barrel temperature of the extruder is set as follows:

‧ Cartridge 0: 35 to 45 ° C

‧ Cartridge 1: 86 to 100 ° C

‧ Cartridge 2 to 5: 180 ° C

‧ Cartridge 6: 120 to 160 ° C

‧ Cartridge 7: 100 to 110 ° C

‧ Head temperature: 100 to 160 ° C

‧ Exit temperature: 148 to 154 ° C

All solid components (phenolic resins used, Oxazoline, stabilizer, antioxidant, flame retardant) - in addition to epoxides and catalysts - mechanically premixed and fed into the extruder via a metering hopper (see Figure 1 (a)) 0. Simultaneously metered are the epoxides from two different storage containers (the storage container with a jacket temperature of 100 ° C, see (k) in Figure 1) and the catalyst solution (see Figure 1). (b)). The catalyst is fed to the melt in a solution having a concentration of 20% to 44% by weight. The extruder output is about 6 kg/h. The melt is removed via a water-cooled belt (see (d) of Fig. 1), pulverized and ground (see (e) of Fig. 1).

The starting materials and their amounts are shown in Table 3.

The extruder effluent was analyzed at regular intervals:

‧ The melting point of the obtained extruder effluent was determined by the method of Tottoli (CH 320388).

‧ Further, a 50% by weight concentration solution of the extruder effluent in 2-butanone was prepared, and the weight fraction of the insoluble matter was determined.

‧ The glass transition temperature T _g was measured by a differential scanning thermal analyzer (DSC). The extruder effluent was heated from 25 ° C to 180 ° C at a heating rate of 10 K / min, annealed or cured in an aluminum vessel at 180 ° C for 6 hours, cooled to 25 ° C at a cooling rate of 10 K / min, and then The glass transition temperature T _{g was} measured according to DIN 73765 by heating to 300 ° C at a heating rate of 10 K/min.

The analytical properties of the comparative examples were also determined using these analytical techniques.

The analysis results of the extruder discharges of Examples 7 to 10 are set forth in Table 4:

The solid portion seen in Example 9 was a flame retardant which was present in a solid state and thus was insoluble in 2-butanone; the properties in the case of Example 10 were similar.

These invention examples show that on the basis of the process of the invention, a prepolymer can be produced by a Lewis adduct or boron trifluoride, which meets the requirements for stability in ketones. These examples show that the prepolymer has a melting point below 120 °C. The material may be pre-fabricated polymer having a glass transition temperature of 181 to 187 deg.] C to T _g.

Invention Example 11:

All solids (phenolic resin, The oxazoline, stabilizer, antioxidant) are mechanically mixed and input to the extruder via a metering hopper (see (a) of Fig. 1) while measuring the catalyst (see (b) of Fig. 1) and A mixture of an epoxide and an impact modifier (a storage container having a jacket temperature of 50 ° C, see (k) of Figure 1). The mixture was produced by heating the impact modifier in a drying oven to 60 ° C and homogenizing it with an epoxide using a screw agitator. The catalyst was supplied to the melt in the form of a 40% by weight solution. The extruder output is about 6 kg/h. The melt is removed via a water-cooled belt, pulverized and ground.

Table 5: Composition of polymeric melts

The prepolymer has a melting range of 68 to 86 °C.

Invention Example 12:

Making 25.39g of 1,3-phenylene double Oxazoline, 20.76 g of phenolic resin (Durez from Sumitomo-Bakelite) 32311), 0.11g of antioxidant (IONOL LC from Raschig) And 0.23g of stabilizer (Cyasorb from Cytec) 3346) Melt in a glass beaker at 140 ° C for about 30 minutes and stir for about 5 minutes. After the melt has cooled to room temperature, it is homogenized by a mortar, melted in a glass beaker at 100 ° C for about 30 minutes and stirred with 2.50 g of epoxide (Epilox from Leuna Harze). P13-20) and 1.0 g of latent catalyst (prepared from monomolar monohydrate p-toluenesulfonic acid (from Merck) and diethanolamine (from Merck), equivalent to 0.64 g = 1.28% monohydrate pair -toluenesulfonic acid) blended. The starting material was stirred for a further 5 minutes and then the melt was allowed to cool to room temperature. The glass transition temperature T _g after curing was 121 ° C, and the curing was carried out at a temperature of 180 ° C for 6 hours. The glass transition temperature T _{g was} determined according to DIN 73765 by a differential scanning thermal analyzer (DSC) heated to 300 ° C at a heating rate of 10 K/min.

A prepolymer having a glass transition temperature _Tg of 121 ° C was obtained using the latent monohydrate p-toluenesulfonic acid / diethanolamine (1.28% mono-p-toluenesulfonic acid).

Invention Example 13:

Making 25.68g of 1,3-phenylene double Oxazoline, 21.00 g of phenolic resin (Durez from Sumitomo-Bakelite) 32311), 0.11g of antioxidant (IONOL LC from Raschig) And 0.23g of stabilizer (Cyasorb from Cytec) 3346) Melt in a glass beaker at 140 ° C for about 30 minutes and stir for about 5 minutes. After the melt has cooled to room temperature, it is homogenized by a mortar, melted in a glass beaker at 100 ° C for about 30 minutes and stirred with 2.50 g of epoxide (Epilox from Leuna Harze). P13-20) and 0.48 g of latent catalyst (prepared from monomolar monohydrate p-toluenesulfonic acid (from Merck) and diethanolamine (from Merck), equivalent to 0.31 g = 0.61% monohydrate pair -toluenesulfonic acid) blended. The starting material was stirred for a further 5 minutes and then the melt was allowed to cool to room temperature. The glass transition temperature T _g after curing was 93.6 ° C, and the curing was carried out at a temperature of 180 ° C for 6 hours. The glass transition temperature T _{g was} determined according to DIN 73765 by a differential scanning thermal analyzer (DSC) heated to 300 ° C at a heating rate of 10 K/min.

A prepolymer having a glass transition temperature _Tg of 93.6 °C was obtained using the latent monohydrate p-toluenesulfonic acid/diethanolamine (0.61% mono-p-toluenesulfonic acid).

Invention Example 14:

Making 25.39g of 1,3-phenylene double Oxazoline, 20.76 g of phenolic resin (Durez from Sumitomo-Bakelite) 32311), 0.11g of antioxidant (IONOL LC from Raschig) And 0.23g of stabilizer (Cyasorb from Cytec) 3346) Melt in a glass beaker at 140 ° C for about 30 minutes and stir for about 5 minutes. After the melt has cooled to room temperature, it is homogenized by a mortar, melted in a glass beaker at 100 ° C for about 30 minutes and stirred with 2.50 g of epoxide (Epilox from Leuna Harze). P13-20) and 1.4 g of latent catalyst (prepared from a molar amount of monohydrate p-toluenesulfonic acid (from Merck) and 1-amino-2-propanol (from Merck), equivalent to 1.0 g = 2% monohydrate p-toluenesulfonic acid) blended. The starting material was stirred for a further 2 minutes, 5.55 g of Exolit AP 422 (flammable agent) was added and the melt was then allowed to cool to room temperature. The glass transition temperature T _g after curing was 113 ° C, and the curing was carried out at a temperature of 140 ° C for 3 hours. This was followed by post-curing at 180 °C for 2 hours, resulting in a glass transition temperature of 144 °C. The glass transition temperature T _{g was} determined according to DIN 73765 by a differential scanning thermal analyzer (DSC) heated to 300 ° C at a heating rate of 10 K/min.

(a). . . Solid component

(b). . . catalyst

(c). . . Product discharge location

(d). . . Water cooled belt

(e). . . Grinding

(f). . . Fine grain

(g). . . Sleeve

(h). . . Screw drive

(i). . . Extruder head

(k). . . Epoxide

0. . . cylinder

1. . . cylinder

2. . . cylinder

3. . . cylinder

4. . . cylinder

5. . . cylinder

6. . . cylinder

7. . . cylinder

Figure 1 is a schematic illustration of a multi-cylinder extruder in accordance with the present invention.

(a). . . Solid component

(b). . . catalyst

(c). . . Product discharge location

(d). . . Water cooled belt

(e). . . Grinding

(f). . . Fine grain

(g). . . Sleeve

(h). . . Screw drive

(i). . . Extruder head

(k). . . Epoxide

0. . . cylinder

1. . . cylinder

2. . . cylinder

3. . . cylinder

4. . . cylinder

5. . . cylinder

6. . . cylinder

7. . . cylinder

Claims (16)

A continuous preparation of a phenolic resin based on the use of an extruder in the presence of a catalyst a method of pre-polymerizing an oxazoline component and an epoxide characterized by the phenolic resin in stream A and An oxazoline component is supplied to the extruder; and a Lewis Lewis adduct of boron trifluoride or aluminum trichloride as a catalyst, or an arylsulfonic acid or alkanesulfonic acid, or a late aromatic sulfonate as a catalyst B An acid or a potential alkane sulfonic acid is supplied to the extruder; and the epoxide is supplied to the extruder in stream C, the lateral feed of the stream A being attached to the stream C when viewed in the direction of extrusion Prior to the infeed, the reactants are mixed at a reaction temperature of 120 to 200 ° C and a residence time of 3 seconds to 15 minutes in the extruder; and then the extruder is 30 to 60 seconds The effluent product is cooled to a temperature of 25 ° C to 45 ° C. A method of claim 1, which uses a multi-barrel extruder. The method of claim 2, wherein the different cylinders of the extruder have different temperatures. The method of claim 3, wherein the cartridge to which the stream A is added, the subsequent cartridge along the extrusion direction, and the cartridge before the product discharge position have a temperature lower than the reaction temperature, and the cartridge therebetween has a reaction temperature. The method of claim 4, wherein the streams B and C are fed, in the direction of extrusion, at a barrel between the cartridge to which the stream A is added and the product discharge position. The method of claim 4, wherein the streams A and B are supplied together into the extruder. The method of claim 1, wherein the epoxide used is a monoepoxide of the following structure Wherein R ⁸ = hydrogen, C _1-3 alkyl, the diepoxide of structure (4) A polyfunctional epoxide wherein R ⁹ and R ¹⁰ = hydrogen and C _1-3 alkyl, R ⁹ and R ¹⁰ may be the same or different, or structure (5) and/or structure (6) Wherein R ¹¹ = hydrogen, C _1-3 alkyl or Wherein R ¹² = hydrogen, C _1-3 alkyl. The method of claim 1, wherein from 1% to 10% by weight of the epoxide is used based on the composition of the components supplied to the extruder. The method of claim 1, wherein one or more stabilizers are added, the stabilizer being a HALS compound (hindered amine light stabilizer). The method of claim 1, wherein one or more antioxidants are added, and the antioxidant is a hindered phenol. The method of claim 1, wherein from 1% to 15% by weight of the impact modifier is used based on the composition of the components supplied to the extruder. The method of claim 1, wherein from 1% to 10% by weight, based on the composition of the components supplied to the extruder, a halogenated or non-halogenated flame retardant is used. A prepolymer obtainable by the method of at least one of claims 1 to 12. For example, the prepolymer of claim 13 is used for the manufacture of materials. The prepolymer of claim 14, wherein the prepolymer is first dissolved in 2-butanone, followed by impregnating a reinforcing fiber selected from glass fibers or carbon fibers with a solution of the prepolymer, and finally curing. The prepolymer of claim 14, wherein the prepolymer is in the form of a powder for use in the manufacture of a prepreg.